Search results for: hydrogen evolution reaction

Authors: Sanjay Upadhyay, Om Prakash Pandey

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Hydrogen has been promoted as an alternative source of energy, which is renewable, cost-effective, and nature-friendly. Hydrogen evolution reaction (HER) can be used for mass production of hydrogen at a very low cost through electrochemical water splitting. An active and efficient electrocatalyst is required to perform this reaction. Till date, platinum (Pt) is a stable and efficient electrocatalyst towards HER. But its high cost and low abundance hiders its large scale uses. Molybdenum carbide having a similar electronic structure to platinum can be a great alternative to costly platinum. In this study, pure phase molybdenum carbide (Mo₂C) has been synthesized in a single step. Synthesis temperature and holding time have been optimized to obtain pure phases of Mo₂C. The surface, structural and morphological properties of as-synthesized compounds have been studied. The HER activity of as-synthesized compounds has been explored in detail.

Keywords: capacitance, hydrogen fuel, molybdenum carbide, nanoparticles

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Authors: Kun-Ting Song, Christian Schott, Peter Schneider, Sebastian Watzele, Regina Kluge, Elena Gubanova, Aliaksandr S. Bandarenka

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The combination of electrochemical impedance spectroscopy (EIS) and the hydrodynamic technique like rotation disc electrode (RDE) provides a critical method for quantitively investigating mechanisms of hydrogen evolution reaction (HER) in acidic and alkaline media. Pt5Gd represented higher HER activities than polycrystalline Pt (Pt(pc)) by means of the surface strain effects. The model of the equivalent electric circuit to fit the impedance data under the RDE configurations is developed. To investigate the relative reaction contribution, the ratio of the charge transfer reactions of the Volmer-Heyrovsky and Volmer-Tafel pathways on Pt and Pt5Gd electrodes is determined. The ratio remains comparably similar in acidic media, but it changes in alkaline media with Volmer–Heyrovsky pathway dominating. This combined approach of EIS and RDE can help to study the electrolyte effects and other essential reactions for electrocatalysis in future work.

Keywords: hydrogen evolution reaction, electrochemical impedance spectroscopy, hydrodynamic methods, electrocatalysis, electrochemical interface

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Authors: Jing Lin, Zou Yiming, Goei Ronn, Li Yun, Amanda Ong Jiamin, Alfred Tok Iing Yoong

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High-entropy alloy (HEA) coatings comprise multiple (five or more) principal elements that give superior mechanical, electrical, and thermal properties. However, the current synthesis methods of HEA coating still face huge challenges in facile and controllable preparation, as well as conformal integration, which seriously restricts their potential applications. Herein, we report a controllable synthesis of conformal quinary HEA coating consisting of noble metals (Rh, Ru, Ir, Pt, and Pd) by using the atomic layer deposition (ALD) with a post-annealing approach. This approach realizes low temperature (below 200 °C), precise control (nanoscale), and conformal synthesis (over complex substrates) of HEA coating. Furthermore, the resulting quinary HEA coating shows promising potential as a platform for catalysis, exhibiting substantially enhanced electrocatalytic hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) performances as compared to other noble metal-based structures such as single metal coating or multi-layered metal composites.

Keywords: high-entropy alloy, thin-film, catalysis, water splitting, atomic layer deposition

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Authors: Burcu Kiren, Alattin CAkan, Nezihe Ayas

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Hydrogen will be arguably the best fuel in the future as it is the most abundant element in the universe. Hydrogen, as a fuel, is notably environmentally benign, sustainable and has high energy content compared to other sources of energy. It can be generated from both conventional and renewable sources. The hydrolysis reaction of metal hydrides provides an option for hydrogen production in the presence of a catalyst. In this study, Ni/dolomite catalyst was synthesized by the wet impregnation method for hydrogen production by hydrolysis reaction of sodium borohydride (NaBH4). Besides, the synthesized catalysts characterizations were examined by means of thermogravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), Brunauer –Emmett – Teller (BET) and scanning electron microscopy (SEM). The influence of reaction temperature (25-75 °C), reaction time (15-60 min.), amount of catalyst (50-250 mg) and active metal loading ratio (20,30,40 wt.%) were investigated. The catalyst prepared with 30 wt.% Ni was noted as the most suitable catalyst, achieving of 35.18% H₂ and hydrogen production rate of 19.23 mL/gcat.min at 25 °C at reaction conditions of 5 mL of 0.25 M NaOH and 100 mg NaBH₄, 100 mg Ni/dolomite.

Keywords: sodium borohydride, hydrolysis, catalyst, Ni/dolomite, hydrogen

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Authors: Yongde Xia, Laicong Deng, Zhuxian Yang

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Developing cost-effective electrocatalysts for oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is vital in energy conversion and storage applications. Herein, we report a simple method for the synthesis of graphene-reinforced cobalt sulfide/carbon nanocomposites and the evaluation of their electrocatalytic performance for typical electrocatalytic reactions. Nanocomposites of cobalt sulfide embedded in N, S co-doped porous carbon and graphene (CoS@C/Graphene) were generated via simultaneous sulfurization and carbonization of one-pot synthesized graphite oxide-ZIF-67 precursors. The obtained CoS@C/Graphene nanocomposite was characterized by X-ray diffraction, Raman spectroscopy, Thermogravimetric analysis-Mass spectroscopy, Scanning electronic microscopy, Transmission electronic microscopy, X-ray photoelectron spectroscopy and gas sorption. It was found that cobalt sulfide nanoparticles were homogenously dispersed in the in-situ formed N, S co-doped porous carbon/Graphene matrix. The CoS@C/10Graphene composite not only shows excellent electrocatalytic activity toward ORR with high onset potential of 0.89 V, four-electron pathway and superior durability of maintaining 98% current after continuously running for around 5 hours, but also exhibits good performance for OER and HER, due to the improved electrical conductivity, increased catalytic active sites and connectivity between the electrocatalytic active cobalt sulfide and the carbon matrix. This work offers a new approach for the development of novel multifunctional nanocomposites for the next generation of energy conversion and storage applications.

Keywords: MOF derivative, graphene, electrocatalyst, oxygen reduction reaction, oxygen evolution reaction, hydrogen evolution reaction

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Authors: Enayat Enayati, Reza Behtash

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The purpose of the H2 removal system is to reduce a content of hydrogen and other combustibles in the CO2 feed owing to avoid developing a possible explosive condition in the synthesis. In order to reduce the possibility of forming an explosive gas mixture in the synthesis as much as possible, the hydrogen percent in the fresh CO2, will be removed in hydrogen converter. Therefore the partly compressed CO2/Air mixture is led through Hydrogen converter (Reactor) where the H2, present in the CO2, is reduced by catalytic combustion to values less than 50 ppm (vol). According the following exothermic chemical reaction: 2H2 + O2 → 2H2O + Heat. The catalyst in hydrogen converter consist of platinum on a aluminum oxide carrier. Low catalyst activity maybe due to catalyst poisoning. This will result in an increase of the hydrogen content in the CO2 to the synthesis. It is advised to shut down the plant when the outlet of hydrogen converter increased above 100 ppm, to prevent undesirable gas composition in the plant. Replacement of catalyst will be time exhausting and costly so as to prevent this, we increase the inlet temperature of hydrogen converter according to following Arrhenius' equation: K=K0e (-E_a/RT) K is rate constant of a chemical reaction where K0 is the pre-exponential factor, E_a is the activation energy, and R is the universal gas constant. Increment of inlet temperature of hydrogen converter caused to increase the rate constant of chemical reaction and so declining the amount of hydrogen from 125 ppm to 70 ppm.

Keywords: catalyst, converter, poisoning, temperature

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Authors: Kishor Kumar Sadasivuni, Mizaj Shabil Sha, Assim Alajali, Godlaveeti Sreenivasa Kumar, Aboubakr M. Abdullah, Bijandra Kumar, Mithra Geetha

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A potential pathway for efficient hydrogen production from water splitting electrolysis involves catalysis or electrocatalysis, which plays a crucial role in energy conversion and storage. Hydrogen generated by electrocatalytic water splitting requires active, stable, and low-cost catalysts or electrocatalysts to be developed for practical applications. In this study, we evaluated combination of 2D materials of NiS nanoparticle catalysts for hydrogen evolution reactions. The photocatalytic H₂ production rate of this nanoparticle is high and exceeds that obtained on components alone. Nanoparticles serve as electron collectors and transporters, which explains this improvement. Moreover, a current density was recorded at reduced working potential by 0.393 mA. Calculations based on density functional theory indicate that the nanoparticle's hydrogen evolution reaction catalytic activity is caused by strong interaction between its components at the interface. The samples were analyzed by XPS and morphologically by FESEM for the best outcome, depending on their structural shapes. Use XPS and morphologically by FESEM for the best results. This nanocomposite demonstrated higher electro-catalytic activity, and a low tafel slope of 60 mV/dec. Additionally, despite 1000 cycles into a durability test, the electrocatalyst still displays excellent stability with minimal current loss. The produced catalyst has shown considerable potential for use in the evolution of hydrogen due to its robust synthesis. According to these findings, the combination of 2D materials of nickel sulfide sample functions as good electocatalyst for H₂ evolution. Additionally, the research being done in this fascinating field will surely push nickel sulfide-based technology closer to becoming an industrial reality and revolutionize existing energy issues in a sustainable and clean manner.

Keywords: electrochemical hydrogenation, nickel sulfide, electrocatalysts, energy conversion, catalyst

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Authors: Kwangho Lee, Joongmyeon Bae

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Fuel cells are spotlighted in the world for being highly efficient and environmentally friendly. A hydrogen fuel for a fuel cell is obtained from a number of sources. Most of fuel cell for APU(Auxiliary power unit) system using diesel fuel as a hydrogen source. Diesel fuel has many advantages, such as high hydrogen storage density, easy to transport and also well-infra structure. However, conventional diesel reforming system for PEMFC(Proton exchange membrane fuel cell) requires a large volume and complex CO removal system for the lower the CO level to less than 10ppm. In addition, the PROX(Preferential Oxidation) reaction cooling load is needed because of the strong exothermic reaction. However, the hydrogen separation membrane that we propose can be eliminated many disadvantages, because the volume is small and permeates only pure hydrogen. In this study, we were conducted to the pressurized diesel reforming and water-gas shift reaction experiment for the hydrogen permeable membrane application.

Keywords: hydrogen, diesel, reforming, ATR, WGS, PROX, membrane, pressure

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Authors: Dina M. Abd El-Aty, D. Aman, E. G. Zaki, Heba M. Salem

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A friendly environmental source of energy as hydrogen was produced by photo-hydrolysis of hydrogen storage material as sodium borohydride (NaBH4), which is non-toxic and stores a high percentage of hydrogen. The photoreaction was produced under visible light and nano-alumina as a catalyst. In this study, we use more economical and friendly environmental oil as a template to produce a nano-catalyst. The prepared catalyst was characterized by X-Ray diffraction, N2-adsorption-desorption, Fourier Transforms Infrared, Scanning Electron microscope and X-Ray Photoelectron Spectroscopy. Different parameters such as catalyst weight, NaBH4 weight and time of irradiation were studied to obtain a highly efficient photo-hydrolysis reaction. The reaction is pseudo-first order and the hydrogen production rate was determined as 1500 ml min-1 g-1 at the optimum conditions.

Keywords: photo-reaction, nano-alumina, hydrogen production, sodium borohydride, visible light

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Authors: Tie-Qing Zhang, Seunghun Jung, Young-Bae Kim

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This research is devoted to developing a membrane reactor to flexibly meet the hydrogen demand of onboard fuel cells, which is an important part of green energy development. Among many renewable chemical products, dimethyl ether (DME) has the advantages of low reaction temperature (400 °C in this study), high hydrogen atom content, low toxicity, and easy preparation. Autothermal reforming, on the other hand, has a high hydrogen recovery rate and exhibits thermal neutrality during the reaction process, so the additional heat source in the hydrogen production process can be omitted. Therefore, the DME auto thermal reforming process was adopted in this study. To control the temperature of the reaction catalyst bed and hydrogen production rate, a Model Predictive Control (MPC) scheme was designed. Taking the above two variables as the control objectives, stable operation of the reformer can be achieved by controlling the flow rates of DME, steam, and high-purity air in real-time. To prevent catalyst poisoning in the fuel cell, the hydrogen needs to be purified to reduce the carbon monoxide content to below 50 ppm. Therefore, a Pd-Ag hydrogen semi-permeable membrane with a thickness of 3-5 μm was inserted into the auto thermal reactor, and the permeation efficiency of hydrogen was improved by steam purging on the permeation side. Finally, hydrogen with a purity of 99.99 was obtained.

Keywords: hydrogen production, auto thermal reforming, membrane, fuel cell

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Authors: Betül Özgenç, Soner Kuşlu, Sabri Çolak, Turan Çalban

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The aim of this study was investigate the leaching kinetics of ulexite in disodium hydrogen phosphate solutions in a mechanical agitation system. Reaction temperature, concentration of disodium hydrogen phosphate solutions, stirring speed, solid/liquid ratio and ulexite particle size were selected as parameters. The experimental results were successfully correlated by linear regression using Statistica program. Dissolution curves were evaluated shrinking core models for solid-fluid systems. It was observed that increase in the reaction temperature and decrease in the solid/liquid ratio causes an increase the dissolution rate of ulexite. The activation energy was found to be 63.4 kJ/mol. The leaching of ulexite was controlled by chemical reaction.

Keywords: ulexite, disodium hydrogen phosphate, leaching kinetics

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Authors: Mr. Liju Elias, A. Chitharanjan Hegde

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Ni-W alloy coatings have been developed galvanostatically on copper substrate from tri-sodium citrate bath, using glycerol as the additive. The deposition conditions for production of Ni-W coatings have been optimized for peak performance of their electrocatalytic activity, namely hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The corrosion behavior of the coatings were tested under working conditions of electrocatalysis (1M KOH). Electrocatalytic behaviours were tested by cyclic voltammetry and chrono-potentiometry techniques. Experimental results demonstrated that Ni-W coatings at low and high current densities (c. d.) showing superior performance for OER and HER respectively. The increased electrocatalytic activity for HER with increase of deposition c. d. was attributed to the phase structure, surface morphology and chemical composition of the coatings, confirmed by XRD, SEM and EDX analysis, respectively. The dependency of hardness and thickness of the coatings on HER and OER were examined, and results were discussed.

Keywords: electrocatalytic behavior, HER, Ni-W alloy, OER

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Authors: Turan Çalban, Nursel Keskin, Sabri Çolak, Soner Kuşlu

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Gypsum (CaSO4.2H2O) is a mineral that is found in large quantities in the Turkey and in the World. The dissolution of this mineral in the diammonium hydrogen phosphate solutions has not been studied so far. Investigation of the dissolution and dissolution kinetics gypsum in diammonium hydrogen phosphate solutions will be useful for evaluating of solid wastes containing gypsum. In this study, parameters such as diammonium hydrogen phosphate concentration, temperature and stirring speed affecting on the dissolution rate of the gypsum in diammonium hydrogen phosphate solutions were investigated. In experimental studies have researched effectiveness of the selected parameters. The dissolution of gypsum were examined in two parts at low and high temperatures. The experimental results were successfully correlated by linear regression using Statistica program. Dissolution curves were evaluated shrinking core models for solid-fluid systems. The activation energy was found to be 34.58 kJ/mol and 44.45 kJ/mol for the low and the high temperatures. The dissolution of gypsum was controlled by chemical reaction both low temperatures and high temperatures. Reaction rate expressions of dissolution of gypsum at the low temperatures and the high temperatures controlled by chemical reaction are as follows, respectively. = k1.e-5159.5/T.t = k2.e-5346.8/T.t Where k1 and k2 are constants depending on the diammonium hydrogen phosphate solution concentration, the solid/liquid ratio, the stirring speed and the particle size.

Keywords: diammonium hydrogen phosphate, dissolution kinetics, gypsum, kinetics.

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Authors: Zhanzhao Fu, Chongyi Ling, Jinlan Wang

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Water splitting and rechargeable air-based batteries are emerging as new renewable energy storage and conversion technologies. However, the discovery of suitable catalysts with high activity and low cost remains a great challenge. In this work, we report a single-atom trifunctional catalyst, namely Ti₃C₂O₂ supported single Pd atom (Pd1@Ti₃C₂O₂), for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). This catalyst is selected from 12 candidates and possesses low overpotentials of 0.22 V, 0.31 V and 0.34 V for the HER, OER and ORR, respectively, making it an excellent electrocatalyst for both overall water splitting and rechargeable air-based batteries. The superior OER and ORR performance originates from the optimal d band center of the supported Pd atom. Moreover, the excellent activity can be maintained even if the single Pd atoms aggregate into small clusters. This work offers new opportunities for advancing the renewable energy storage and conversion technologies and paves a new way for the development of multifunctional electrocatalysts.

Keywords: DFT, SACs, OER, ORR, HER

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Authors: Chongsutthamani Sitthiwet, Praphatsorn Plerdsranoy, Palmarin Dansirima, Priew Eiamlamai, Oliver Utke, Rapee Utke

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Hydrogen storage tank containing compacted LiNH2-LiH is developed by doping with TiF₄ and multi-walled nanotubes (MWCNTs) to study kinetic properties. Transition metal-based catalyst (TiF₄) provides the catalytic effect on hydrogen dissociation/recombination, while MWCNTs benefit thermal conductivity and hydrogen permeability during de/rehydrogenation process. The Enhancement of dehydrogenation kinetics is observed from the single-step reaction at a narrower and lower temperature range of 150-350 ºC (100 ºC lower than the compacted LiNH₂-LiH without additives) as well as long plateau temperature and constant hydrogen flow rate (50 SCCM) up to 30 min during desorption. Besides, Hydrogen contents de/absorbed during 5-6 cycles increase from 1.90-2.40 to 3.10-4.70 wt. % H₂ (from 29 to up to 80 % of theoretical capacity). In the process, Li₅TiN₃ is detected upon cycling probably absorbs NH₃ to form Li₅TiN₃(NH₃)x, which is favoring hydrogen sorption properties of the LiNH₂-LiH system. Importantly, the homogeneous reaction mechanisms and performances are found at all positions inside the tank of compacted LiNH₂-LiH doped with TiF₄ and MWCNTs.

Keywords: carbon, hydride, kinetics, dehydrogenation

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Authors: Horng-Wen Wu, Yi Chao, Rong-Fang Horng

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This study is to develop a methanol steam reformer with a heat recovery zone, which recovers heat from exhaust gas of a diesel engine, and to investigate waste heat recovery ratio at the required reaction temperature. The operation conditions of the reformer are reaction temperature (200 °C, 250 °C, and 300 °C), steam to carbonate (S/C) ratio (0.9, 1.1, and 1.3), and N2 volume flow rate (40 cm3/min, 70 cm3/min, and 100 cm3/min). Finally, the hydrogen concentration, the CO, CO2, and N2 concentrations are measured and recorded to calculate methanol conversion efficiency, hydrogen flow rate, and assisting combustion gas and impeding combustion gas ratio. The heat source of this reformer comes from electric heater and waste heat of exhaust gas from diesel engines. The objective is to recover waste heat from the engine and to make more uniform temperature distribution within the reformer. It is beneficial for the reformer to enhance the methanol conversion efficiency and hydrogen-rich gas production. Experimental results show that the highest hydrogen flow rate exists at N2 of the volume rate 40 cm3/min and reforming reaction temperature of 300 °C and the value is 19.6 l/min. With the electric heater and heat recovery from exhaust gas, the maximum heat recovery ratio is 13.18 % occurring at water-methanol (S/C) ratio of 1.3 and the reforming reaction temperature of 300 °C.

Keywords: heat recovery, hydrogen-rich production, methanol steam reformer, methanol conversion efficiency

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Authors: Sony, Ashok N. Bhaskarwar

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Production of hydrogen from a renewable raw material without any co-synthesis of harmful greenhouse gases is the current need for sustainable energy solutions. The sulfur-iodine (SI) thermochemical cycle, using intermediate chemicals, is an efficient process for producing hydrogen at a much lower temperature than that required for the direct splitting of water. No net byproduct forms in the cycle. Hydrogen iodide (HI) decomposition is a crucial reaction in this cycle, as the product, hydrogen, forms only in this step. It is an endothermic, reversible, and equilibrium-limited reaction. The theoretical equilibrium conversion at 550°C is just a meagre of 24%. There is a growing interest, therefore, in enhancing the HI conversion to near-equilibrium values at lower reaction temperatures and by possibly improving the rate. The reaction is relatively slow without a catalyst, and hence catalytic decomposition of HI has gained much significance. Bi-metallic Ni-Co, Ni-Mn, Co-Mn, and tri-metallic Ni-Co-Mn catalysts over zirconia support were tested for HI decomposition reaction. The catalysts were synthesized via a sol-gel process wherein Ni was 3wt% in all the samples, and Co and Mn had equal weight ratios in the Co-Mn catalyst. Powdered X-ray diffraction and Brunauer-Emmett-Teller surface area characterizations indicated the polycrystalline nature and well-developed mesoporous structure of all the samples. The experiments were performed in a vertical laboratory-scale packed bed reactor made of quartz, and HI (55 wt%) was fed along with nitrogen at a WHSV of 12.9 hr⁻¹. Blank experiments at 500°C for HI decomposition suggested conversion of less than 5%. The activities of all the different catalysts were checked at 550°C, and the highest conversion of 23.9% was obtained with the tri-metallic 3Ni-Co-Mn-ZrO₂ catalyst. The decreasing order of the performance of catalysts could be expressed as: 3Ni-Co-Mn-ZrO₂ > 3Ni-2Co-ZrO₂ > 3Ni-2Mn-ZrO₂ > 2.5Co-2.5Mn-ZrO₂. The tri-metallic catalyst remained active till 360 mins at 550°C without any observable drop in its activity/stability. Among the explored catalyst compositions, the tri-metallic catalyst certainly has a better performance for HI conversion when compared to the bi-metallic ones. Owing to their low costs and ease of preparation, these trimetallic catalysts could be used for large-scale hydrogen production.

Keywords: sulfur-iodine cycle, hydrogen production, hydrogen iodide decomposition, bi-, and tri-metallic catalysts

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Authors: Francisco Espinosa, Juan Chavarría

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Glycerol is a byproduct of biodiesel production that can be used for aqueous-phase reforming to obtain hydrogen. Iridium is a material that has high activity and hydrogen selectivity for steam phase reforming. Nevertheless, a drawback for the use of iridium in aqueous-phase reforming is the low activity in water-gas shift reaction. Therefore, in this work, it is proposed the use of nickel and copper as a second metal in the catalyst to reach a synergetic effect. Iridium, iridium-nickel and iridium-copper catalysts were prepared by incipient wetness impregnation and evaluated in the aqueous-phase reforming of glycerol using CeO₂ or La₂O₃ as support. The catalysts were characterized by XRD, XPS, and EDX. The reactions were carried out in a fixed bed reactor feeding a solution of glycerol 10 wt% in water at 270°C, and reaction products were analyzed by gas chromatography. It was found that IrNi/CeO₂ reached highest glycerol conversion and hydrogen production, slightly above 70% and 43 vol% respectively. In terms of conversion, iridium is a promising metal, and its activity for hydrogen production can be enhanced when adding a second metal.

Keywords: aqueous-phase reforming, glycerol, hydrogen production, iridium

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Authors: Juree Hong, Sanggeun Lee, Jungmok Seo, Taeyoon Lee

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We report a facile synthesis of metal nano particles (NPs) on graphene layer via galvanic displacement reaction between graphene-buffered copper (Cu) and metal ion-containing salts. Diverse metal NPs can be formed on graphene surface and their morphologies can be tailored by controlling the concentration of metal ion-containing salt and immersion time. The obtained metal NP-decorated single-layer graphene (SLG) has been used as hydrogen gas (H2) sensing material and exhibited highly sensitive response upon exposure to 2% of H2.

Keywords: metal nanoparticle, galvanic displacement reaction, graphene, hydrogen sensor

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Authors: Mohamed A. Deyab, Omnia A. A. El-Shamy

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The purpose of this study is to reveal on the systematic evaluation of hydrogen production by aluminum hydrolysis in alkaline solutions containing different surfactants using hydrogen evolution measurements and supplemented by scan electron microscope (SEM) and energy dispersive X-ray analysis (EDX). It has been demonstrated that when alkaline concentration and solution temperature rise, the rate of H2 generation and, consequently, aluminum hydrolysis also rises. The addition of nonionic and cationic surfactants solution retards the rate of H2 production. The work is a promising option for carbon-free hydrogen production from renewable resources.

Keywords: energy, hydrogen, hydrolysis, surfactants

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Authors: Saroj Poudel, Joshua Mancini, Douglas Pike, Jennifer Timm, Alexei Tyryshkin, Vikas Nanda, Paul Falkowski

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On the early Earth, protein-metal complexes likely harvested energy from a reduced environment. These complexes would have been precursors to the metabolic enzymes of ancient organisms. Hydrogenase is an essential enzyme in most anaerobic organisms for the reduction and oxidation of hydrogen in the environment and is likely one of the earliest evolved enzymes. To attempt to reinvent a precursor to modern hydrogenase, we computationally designed a short thirteen amino acid peptide that binds the often-required catalytic transition metal Nickel in hydrogenase. This simple complex can achieve hundreds of hydrogen evolution cycles using light energy in a broad range of temperature and pH. Biophysical and structural investigations strongly indicate the peptide forms a di-nickel active site analogous to Acetyl-CoA synthase, an ancient protein central to carbon reduction in the Wood-Ljungdahl pathway and capable of hydrogen evolution. This work demonstrates that prior to the complex evolution of multidomain enzymes, early peptide-metal complexes could have catalyzed energy transfer from the environment on the early Earth and enabled the evolution of modern metabolism

Keywords: hydrogenase, prebiotic enzyme, metalloenzyme, computational design

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Authors: Yang Li, Mingkai Liu, Qiong Rao, Zhongrui Gai, Ying Pan, Hongguang Jin

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Hydrogen is an ideal and potential energy carrier due to its high energy efficiency and low pollution. An alternative and promising approach to hydrogen generation is the chemical looping steam reforming of methane (CL-SRM) over iron-based oxygen carriers. However, the process faces challenges such as high reaction temperature (>850 ℃) and low methane conversion. We demonstrate that Ni-mixed Fe-based oxygen carrier particles have significantly improved the methane conversion and hydrogen production rate in the range of 450-600 ℃ under atmospheric pressure. The effect on the reaction reactivity of oxygen carrier particles mixed with different Ni-based particle mass ratios has been determined in the continuous unit. More than 85% of methane conversion has been achieved at 600 ℃, and hydrogen can be produced in both reduction and oxidation steps. Moreover, the iron-based oxygen carrier particles exhibited good cyclic performance during 150 consecutive redox cycles at 600 ℃. The mid-temperature iron-based oxygen carrier particles, integrated with a moving-bed chemical looping system, might provide a powerful approach toward more efficient and scalable hydrogen production.

Keywords: chemical looping, hydrogen production, mid-temperature, oxygen carrier particles

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Authors: Ghazi R. Reda Mahmoud Reda

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Among the metal that forms hydride´s, Mg and Ti are known as the most lightweight materials; however, they are covered with a passive layer of oxides and hydroxides and require activation treatment under high temperature ( > 300 C ) and hydrogen pressure ( > 3 MPa) before being used for storage and transport applications. It is well known that small graphite addition to Ti or Mg, lead to a dramatic change in the kinetics of mechanically induced hydrogen sorption ( uptake) and significantly stimulate the Ti-Hydrogen interaction. Many explanations were given by different authors to explain the effect of graphite addition on the performance of Ti as material for hydrogen storage. Not only graphite but also the addition of a polycyclic aromatic compound will also improve the hydrogen absorption kinetics. It will be shown that the function of carbon addition is two-fold. First carbon acts as a vacuum cleaner, which scavenges out all the interstitial oxygen that can poison or slow down hydrogen absorption. It is also important to note that oxygen favors the chemisorption of hydrogen, which is not desirable for hydrogen storage. Second, during scavenging of the interstitial oxygen, the carbon reacts with oxygen in the nano and microchannel through a highly exothermic reaction to produce carbon dioxide and monoxide which provide the necessary heat for activation and thus in the presence of carbon lower heat of activation for hydrogen absorption which is observed experimentally. Furthermore, the product of the reaction of hydrogen with the carbon oxide will produce water which due to ball milling hydrolyze to produce the linear H5O2 + this will reconstruct the primary structure of the nanocarbon to form secondary structure, where the primary structure (a sheet of carbon) are connected through hydrogen bonding. It is the space between these sheets where physisorption or defect mediated sorption occurs.

Keywords: metal forming hydrides, polar molecule impurities, titanium, phase diagram, hydrogen absorption

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Authors: Motonori Tamura

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The hydrogen barrier properties of the coatings of diamond-like carbon (DLC) were evaluated. Using plasma chemical vapor deposition and sputtering, DLC coatings were deposited on Type 316L stainless steels. The hydrogen permeation rate was reduced to 1/1000 or lower by the DLC coatings. The DLC coatings with high hydrogen content had high hydrogen barrier function. For hydrogen diffusion in coatings, the movement of atoms through hydrogen trap sites such as pores in coatings, and crystal defects such as dislocations, is important. The DLC coatings are amorphous, and there are both sp3 and sp2 bonds, and excess hydrogen could be found in the interstitial space and the hydrogen trap sites. In the DLC coatings with high hydrogen content, these hydrogen trap sites are likely already filled with hydrogen atoms, and the movement of new hydrogen atoms could be limited.

Keywords: hydrogen permeation, stainless steels, diamond-like carbon, hydrogen trap sites

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Authors: V. Pérez-Herranz, C. González-Buch, E. M. Ortega, S. Mestre

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In this work new macroporous Ni electrodes modified with Au nanoparticles for hydrogen production have been developed. The supporting macroporous Ni electrodes have been obtained by means of the electrodeposition at high current densities. Then, the Au nanoparticles were synthesized and added to the electrode surface. The electrocatalytic behaviour of the developed electrocatalysts was studied by means of pseudo-steady-state polarization curves, electrochemical impedance spectroscopy (EIS) and hydrogen discharge curves. The size of the Au synthetized nanoparticles shows a monomodal distribution, with a very sharp band between 10 and 50 nm. The characteristic parameters d10, d50 and d90 were 14, 20 and 31 nm respectively. From Tafel polarization data has been concluded that the Au nanoparticles improve the catalytic activity of the developed electrodes towards the HER respect to the macroporous Ni electrodes. EIS permits to obtain the electrochemically active area by means of the roughness factor value. All the developed electrodes show roughness factor values in the same order of magnitude. From the activation energy results it can be concluded that the Au nanoparticles improve the intrinsic catalytic activity of the macroporous Ni electrodes.

Keywords: Au nano particles, hydrogen evolution reaction, porous Ni electrodes, electrochemical impedance spectroscopy

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Authors: Hamad Almohamadi, Nabeel Alharthi, Majed Alamoudi

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Biphasic electrodes featuring CuSx/NiSx electrodeposited on nickel foam have been investigated for their electrocatalytic activity in water splitting. The study investigates the impacts of an S-vacancy induced biphasic design on the overpotential and Tafel slope. According to the findings, the NiSx/CuSx/NF electrode with S-vacancy defects displays stronger oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) activity with lower overpotential and a steeper Tafel slope than the non-defect sample. NiSx/CuSx/NF exhibits the lowest overpotential value of 212 mV vs reversible hydrogen electrode (RHE) for OER and −109 mV vs RHE for HER at 10 mA cm−2. Tafel slope of 25.4 mV dec−1 for OER and −108 mV dec−1 for OER found of that electrode. The electrochemical surface area (ECSA) and diffusion impedance of the electrode is calculated. The maximum ECSA, lowest series resistance and lowest charge transfer resistance are found in the *NiSx/CuSx/NF sample with S-vacancy defects, showing increased electrical conductivity and quick charge transfer kinetics. The *NiSx/CuSx/NF electrode was found to be stable for 80 hours in pure water splitting and 20 hours in sea-water splitting. The investigation comes to the conclusion that the enhanced water splitting activity and electrical conductivity of the electrode are caused by S-vacancy defects resulting in improved water splitting performance.

Keywords: water splitting, electrocatalyst, biphasic design, electrodeposition

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Authors: Hamidreza Sahaleh

Abstract:

Because of the stringent prerequisite of low sulfur and heavier raw oil feedstock more hydrogen will be devoured in the refineries. Specifically if huge scale limits are the reaction to an expanded hydrogen request, certain configuration and building background are obliged with, which will be depicted in this paper with an illustration. Chosen procedure plan prerequisite will be recorded and portrayed in agreement to the flowsheet. Also, a determination of imaginative outline elements, similar to process condensate reuse, safe reformer start up and prerequisites will be highlighted.

Keywords: low sulfur, raw oil, refineries, flowsheet

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Authors: Mohamed A. Deyab, Ahmed E. Awadallah

Abstract:

Under various conditions, we present a promising method for producing pure hydrogen energy from the electrochemical reaction of Mg metal in waste oilfield water (WOW). Mg metal and WOW are primarily consumed in this process. The results show that the hydrogen gas output is highly dependent on temperature and solution pH. The best conditions for hydrogen production were found to be a low pH (2.5) and a high temperature (338 K). For the first time, the Allyl methylimidazolium bis-trifluoromethyl sulfonyl imide) (IL) ionic liquid is used to regulate the rate of hydrogen generation. It has been confirmed that increasing the solution temperature and decreasing the solution pH accelerates Mg dissolution and produces more hydrogen per unit of time. The adsorption of IL on the active sites of the Mg surface is unrestricted by mixing physical and chemical orientation. Inspections using scanning electron microscopy (SEM), energy dispersive X-ray (EDX), and FT-IR spectroscopy were used to identify and characterise surface corrosion of Mg in WOW. This process is also completely safe and can create energy on demand.

Keywords: hydrogen production, Mg, wastewater, ionic liquid

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Authors: Deepti Mishra, Arindam Modak, K. K. Pant, Xiu Song Zhao

Abstract:

The promotional effect of mixed ceria-zirconia oxides (CZO) over the Mo/HZSM-5 catalyst for methane dehydroaromatization (MDA) reaction was studied. The surface and structural properties of the synthesized catalyst were characterized using a range of spectroscopic and microscopic techniques, and the correlation between catalytic properties and its performance for MDA reaction is discussed. The impregnation of CZO solid solution on Mo/HZSM-5 was observed to give an excellent catalytic performance and improved benzene formation rate (4.5 μmol/gcat. s) as compared to the conventional Mo/HZSM-5 (3.1 μmol/gcat. s) catalyst. In addition, a significant reduction in coke formation was observed in the CZO-modified Mo/HZSM-5 catalyst. The prevailing comprehension for higher catalytic activity could be because of the redox properties of CZO deposited Mo/HZSM-5, which acts as a selective oxygen supplier and performs hydrogen combustion during the reaction, which is indirectly probed by O₂-TPD and H₂-TPR analysis. The selective hydrogen combustion prevents the over-oxidation of aromatic species formed during the reaction while the generated steam helps in reducing the amount of coke generated in the MDA reaction. Thus, the advantage of CZO incorporated Mo/HZSM-5 is manifested as it promotes the reaction equilibrium to shift towards the formation of benzene which is favourable for MDA reaction.

Keywords: Mo/HZSM-5, ceria-zirconia (CZO), in-situ combustion, methane dehydroaromatization

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Authors: Blaž Likozar, Andraž Pavlišič, Matic Pavlin, Taja Žibert, Aleksandra Zamljen, Sašo Gyergyek, Matej Huš

Abstract:

Ammonia is gaining recognition as a carbon-free fuel for energy-intensive applications, particularly transportation, industry, and power generation. Due to its physical properties, high energy density of 3 kWh kg-1, and high gravimetric hydrogen capacity of 17.6 wt%, ammonia is an efficient energy vector for green hydrogen, capable of mitigating hydrogen’s storage, distribution, and infrastructure deployment limitations. Chemicalstorage in the form of ammonia provides an efficient and affordable solution for energy storage, which is currently a critical step in overcoming the intermittency of abundant renewable energy sources with minimal or no environmental impact. Experiments were carried out to validate the modelling in a packed bed reactor, which proved to be agreeing.

Keywords: hydrogen, ammonia, catalysis, modelling, kinetics

Procedia PDF Downloads 21